Transferability of the SRP32-vdW specific reaction parameter functional to CHD3 dissociation on Pt(110)-(2 x 1)
Transferability of the SRP32-vdW specific reaction parameter functional to CHD3 dissociation on Pt(110)-(2 x 1)
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DOI：
10.1063/1.5081005
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发表时间：
2019-03-28
影响因子：
4.4
通讯作者：
Kroes, Geert-Jan
中科院分区：
文献类型：
--
作者：
Chadwick, Helen;Gutierrez-Gonzalez, Ana;Kroes, Geert-Jan
阶梯过渡金属表面，包括重建的Pt（110）-（2 x 1）表面，可用于模拟线缺陷对催化剂的影响。我们提出了一个相结合的实验和理论研究CHD 3解离在这个表面上。理论预测的初始粘附系数，S-0，从从头算分子动力学计算使用特定的反应参数（SRP）的密度泛函（DF）理论的方法，而测量的粘附系数得到使用国王和威尔斯方法。此处使用的SRP DF先前已针对Pt（111）上的甲烷解离而导出，使得实验测试该SRP DF到甲烷+ Pt（110）-（2 X 1）的可转移性。实验和计算的S-0之间的一致性较差，理论和测量的反应性之间的平均能量偏移为20 kJ/mol。有两个因素可能会导致这种差异，其中第一个是，有一个很大的不确定性，由于大量的分子被困在表面上的1 ps的传播时间结束时，在计算的粘附系数。第二个是SRP 32-vdW泛函可能无法准确描述Pt（110）-（2 x 1）表面。在这里考虑的最低入射能量下，Pt（110）-（2 x 1）比平坦的Pt（111）表面更具反应性，但在高于100 kJ/mol的入射能量下情况相反。由AIP Publishing授权出版。
Stepped transition metal surfaces, including the reconstructed Pt(110)-(2 x 1) surface, can be used to model the effect of line defects on catalysts. We present a combined experimental and theoretical study of CHD3 dissociation on this surface. Theoretical predictions for the initial sticking coefficients, S-0, are obtained from ab initio molecular dynamics calculations using the specific reaction parameter (SRP) approach to density functional (DF) theory, while the measured sticking coefficients were obtained using the King and Wells method. The SRP DF used here had been previously derived for methane dissociation on Pt(111) so that the experiments test the transferability of this SRP DF to methane + Pt(110)-(2 x 1). The agreement between the experimental and calculated S-0 is poor, with the average energy shift between the theoretical and measured reactivities being 20 kJ/mol. There are two factors which may contribute to this difference, the first of which is that there is a large uncertainty in the calculated sticking coefficients due to a large number of molecules being trapped on the surface at the end of the 1 ps propagation time. The second is that the SRP32-vdW functional may not accurately describe the Pt(110)-(2 x 1) surface. At the lowest incident energies considered here, Pt(110)-(2 x 1) is more reactive than the flat Pt(111) surface, but the situation is reversed at incident energies above 100 kJ/mol. Published under license by AIP Publishing.